Novel pattern formation in the collapse process of floating monolayer at the air-water interface

We have observed a remarkable two-armed spiral in the collapse process of a floating monolayer at the air-water interface by phase contrast microscopy. This demonstrates that the floating monolayer as a form of soft condensed matter reorganizes itself due to a certain kind of macroscopic or collective behavior of molecules as it collapses. This pattern formation is caused by the breakdown of a critical dynamical balance between the deformation of solid domain and the applied surface pressure. The fragility as well as the flexibility of the floating monolayer can be associated with the observed pattern growth. There are also observed interesting, periodically arranged collections of molecules in numerous collapsed regions. Received: 8 July 1997 / Accepted: 4 November 1997     

Peroxyoxalate chemiluminescence detection of condensates of malondialdehyde with thiobarbituric acids using a flow system.

The peroxyoxalate chemiluminescence(CL) detection method for the evaluation of the CL intensity of malondialdehyde(MDA) condensates with seven 2-thiobarbituric acid derivatives is described. The method consists of a flow injection technique together with a CL detection system using bis(2,4,6-trichlorophenyl) oxalate(TCPO) and hydrogen peroxide as chemiluminogenic reagents. Linear correlations between CL intensity and concentration are obtained for pmol levels of condensates. Among the condensates, 1,3-diethyl-2-thiobarbituric acid(DETBA)-MDA shows the largest CL intensity. High performance liquid chromatography (HPLC)/CL detection of DETBA-MDA and 1,3-diphenyl-2-thiobarbituric acid(DPTBA)-MDA using a mixture of TCPO and hydrogen peroxide in acetonitrile as a postcolumn reagent solution is also described. The detection limits for DETBA-MDA and DPTBA-MDA are 20 and 200 fmol, respectively, per 20 microL injection at a signal-to-noise ratio of 2. This HPLC/CL detection system was applied to the determination of MDA in rat brains by using DETBA as a fluorescent derivatizing reagent.     

Microdetermination of hyaluronic acid in human urine by high performance liquid chromatography.

A high performance liquid chromatographic (HPLC) system is described for determination of the unsaturated disaccharide (delta Di-HA) derived from hyaluronic acid (HA) in human urine by digestion with hyaluronidase SD. The effects of eluents on the separation of delta Di-HA and delta Di-0S, which is derived from the reaction of chondroitin with the enzyme, have been studied. The established chromatographic conditions were as follows--column: a stainless steel tube (4 mm i.d. x 250 mm) packed with TSKgel NH2-60; eluent: a mixture of acetonitrile and 0.1 M Tris-HCl buffer containing 0.1 M boric acid and 10 mM sodium sulphate, pH 7.0 (64:36, v/v). The strong fluorescence of unsaturated disaccharide after the reaction with 2-cyanoacetamide in alkaline medium was used for post-column detection. The calibration curve for delta Di-HA was linear in the range 5 pmol-5nmol with a practical detection limit of 2 pmol. The assay coefficients of variation (n = 5) at 200 pmol for delta Di-HA and delta Di-0S were 1.7 and 1.5%, respectively. This HPLC system has been applied to the determination of HA in human urine.     

Experimental consequences ofSU(3) symmetry in ans d g Boson Model

Energies of collective levels in¹⁷⁸Hf and²³⁴U are compared with predictions of theSU (3) limit of thesdg Interacting Boson Model. All known positive parity states of¹⁷⁸Hf below 1.8 MeV (with the exception of a 0⁺ band) have been satisfactorily reproduced. Most of the bands in²³⁴U are also described by the model. However, a few predicted states have no experimental counterpart. The introduction of theg-bosons strongly reduces the previously observed discrepancies between experimentalB(E2)'s in²³⁸U and thesd-IBM calculation.     

Enzyme-less amperometric biosensor for l-ascorbate using poly-l-histidine-copper complex as an alternative biocatalyst

A poly-l-histidine(PLH)-copper(II) complex can be used as an alternative biocatalyst in an O(2) detection-type amperometric enzyme-less l-ascorbate (AsA) sensor. The PLH-Cu(II) membrane was simply prepared by entrapping the PLH in polyacrylamide gel and subsequent treatment of the gel with CuCl(2) solution. This enzyme-less biosensor can be used over a relatively wide pH region from 4 to 11 and enables precise determination of AsA (RSD less than 3%, n=10) at pH 7.0. The fundamental performance characteristics (sensitivity, response time, and linear range) of this PLH-Cu(II)-based sensor is comparable to those of a native ascorbate oxidase-based sensor. Unfortunately, the selectivity is inherently rather low and, as a result, the response was degraded in the presence of higher concentrations (more than mM order) of quinones. However, reducing sugars caused no interference and the sensor could be used to detect AsA in some fruits and drinks. This enzyme-less sensor has excellent stability for at least 3 months of repeated analysis (more than 300 samples) without loss of ordinal activity.     

Rapid determination of sulphonamides in milk using liquid chromatographic separation and fluorescamine derivatization.

A simple and selective method is presented for the multiple residue determination of eight sulphonamides in consumers' milk. The drugs are sulphisomidine (ID), sulphadiazine (DZ), sulphamerazine, sulphadimidine, sulphamonomethoxine, sulphamethoxazole, sulphadimethoxine and sulphaquinoxaline (SQ). The milk sample was deproteinized with the same volume of 2 M hydrochloric acid and filtered. A 1-ml volume of the filtrate was mixed with 1 ml each of 1.25 M sodium acetate solution and a buffer (pH 3.0) for derivatization with 0.6 ml of 0.02% fluorescamine solution in acetone. A high-performance liquid chromatographic analysis was carried out on a C18 column with a mobile phase of acetonitrile-2% acetic acid (3:5) at 55 degrees C using a fluorescence detector at an excitation wavelength of 405 nm and an emission wavelength of 495 nm. Average recoveries at fortification levels of 2, 5 and 10 ng/ml were 114%, 109% and 106%, respectively. Relative standard deviations were 1-4% at 10 ng/ml for ID, 5 ng/ml for DZ and SQ and 2.5 ng/ml for the other five sulphonamides. The method was applied to 25 milk samples and all appeared to be free from the drugs.     

Myoglobin-CO substate structures and dynamics: multidimensional vibrational echoes and molecular dynamics simulations

Spectrally resolved infrared stimulated vibrational echo data were obtained for sperm whale carbonmonoxymyoglobin (MbCO) at 300 K. The measured dephasing dynamics of the CO ligand are in agreement with dephasing dynamics calculated with molecular dynamics (MD) simulations for MbCO with the residue histidine-64 (His64) having its imidazole epsilon nitrogen protonated (N(epsilon)-H). The two conformational substate structures B(epsilon) and R(epsilon) observed in the MD simulations are assigned to the spectroscopic A(1) and A(3) conformational substates of MbCO, respectively, based on the agreement between the experimentally measured and calculated dephasing dynamics for these substates. In the A(1) substate, the N(epsilon)-H proton and N(delta) of His64 are approximately equidistant from the CO ligand, while in the A(3) substate, the N(epsilon)-H of His64 is oriented toward the CO, and the N(delta) is on the surface of the protein. The MD simulations show that dynamics of His64 represent the major source of vibrational dephasing of the CO ligand in the A(3) state on both femtosecond and picosecond time scales. Dephasing in the A(1) state is controlled by His64 on femtosecond time scales, and by the rest of the protein and the water solvent on longer time scales.     

Studies on the constituents of Anaxagorea luzonensis A. GRAY

Five new xanthones, 1,3,6-trihydroxy-5-methoxy-4-prenylxanthone (1), 1,3,5-trihydroxy-6-methoxy-2-prenylxanthone (2), 1,3,5-trihydroxy-4-(3-hydroxy-3-methylbutyl) xanthone (3), 1,3,6-trihydroxy-4-prenylxanthone (4), 3,6-dihydroxy-1,5-dimethoxyxanthone (5) and one new flavonoid, 3,5,7,4'-tetrahydroxy-2'-methoxyflavone (6) along with seven known xanthones and seven known flavonoids were isolated from the bark of Anaxagorea luzonensis A. GRAY and their chemical structures were determined by means of chemical and spectral studies. Almost all flavonoids and one xanthone (13) showed antioxidant activity.     

Novel syntheses of 2,3-dihydro-5H-1,4-benzoxathiepins and 1,2,3,5-tetrahydro-4,1-benzothiazepines

2,3-Dihydro-5H-1,4-benzoxathiepins were prepared by intramolecular Friedel-Crafts reactions of ethyl α-[2-(aryloxy)ethylthio]-α-chloroacetates or by acid-catalyzed cyclizations of ethyl α-[2-(aryloxy)ethylsulfinyl]-acetate. 1,2,3,5-Tetrahydro-4,1-benzothiazepines were similarly prepared.     

Carrier generation process on photoconductive polymer films as studied by magnetic field effects on the charge-transfer fluorescence and photocurrent

We have studied the magnetic field effects (MFEs) on the charge-transfer fluorescence and transient photocurrent of a 1,2,4,5-tetracyanobenzene-doped poly(N-vinylcarbazole) film, which reflect the recombination and escape yields of the carriers, respectively. The recombination yield dependence of the external magnetic field (B) clearly shows two types of the MFEs, growth with increasing B due to the hyperfine mechanism (HFM) and a negative dip due to the level-crossing mechanism (LCM). On the other hand, the escape yield indicates complementary MFEs with a sharp decrease in yield with increasing B and then a positive dip. Simultaneous observation of the HFM- and LCM-MFEs proves the stepwise hole-hopping mechanism rather the long-range hole-jumping one. The quantitative analysis of the recombination and escape MFEs is performed using the stochastic Liouville equations (SLE) for a one-dimensional lattice model in which the stepwise hole hops take place between the nearest neighbor carbazole units with spin conservation. The SLE analysis provides the recombination and hole transfer rate constants of 7.0 x 10(7) and 4.5 x 10(8) s(-1), respectively. The boundary site number for the ion pairs in the one-dimensional model is estimated by the best fit to the experimental results. The interionic distance of the boundary ion pair in the one-dimensional model including eight sites agrees with the thermalization distance in the Onsager model. Hence, it is concluded that the elementary processes in the Onsager model applied to molecular amorphous solids are the stepwise hole hops rather than a long-range hole jump.